EP3908617B1 - Herstellung von polyurethanhartschaum - Google Patents

Herstellung von polyurethanhartschaum Download PDF

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Publication number
EP3908617B1
EP3908617B1 EP19824290.1A EP19824290A EP3908617B1 EP 3908617 B1 EP3908617 B1 EP 3908617B1 EP 19824290 A EP19824290 A EP 19824290A EP 3908617 B1 EP3908617 B1 EP 3908617B1
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Prior art keywords
polyether
foam
composition according
siloxanes
polyalkylsiloxanes
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EP19824290.1A
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German (de)
English (en)
French (fr)
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EP3908617A1 (de
Inventor
Martin Glos
Jobst Grimminger
Michael Ferenz
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Evonik Operations GmbH
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Evonik Operations GmbH
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Priority to SI201930818T priority Critical patent/SI3908617T1/sl
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/10—Rigid foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention is in the field of rigid polyurethane foams.
  • it relates to the production of rigid polyurethane foams using special siloxane compounds, as well as the use of the foams produced therewith.
  • polyurethane is understood to mean in particular a product obtainable by reacting polyisocyanates and polyols or compounds with isocyanate-reactive groups.
  • other functional groups can also be formed, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and/or uretimines.
  • PU in the context of the present invention is understood to mean both polyurethane and polyisocyanurate, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretimine groups.
  • polyurethane foam is understood to mean in particular foam that is obtained as a reaction product based on polyisocyanates and polyols or compounds with isocyanate-reactive groups.
  • other functional groups can also be formed, such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretimines.
  • Cell-stabilizing additives are used in the production of polyurethane and polyisocyanurate rigid foams to ensure a fine-cell, uniform and low-interference foam structure and thus have a significant positive effect on the performance properties, particularly the thermal insulation capacity of the rigid foam.
  • Surfactants based on polyether-modified siloxanes are particularly effective and are therefore the preferred type of foam stabilizer.
  • PES Polyethersiloxane foam stabilizers
  • the EP 0 570 174 B1 describes polyether siloxanes which are suitable for the production of rigid polyurethane foams using organic blowing agents, in particular chlorofluorocarbons such as CFC-11.
  • the EP 0 877 045 B1 describes analogous structures for this manufacturing process, which differ from the first-mentioned foam stabilizers by a comparatively higher molecular weight and by the combination of two polyether substituents on the siloxane chain.
  • EP1544235 describes typical polyether-modified siloxanes for PU rigid foam applications. Siloxanes with 60 to 130 Si atoms and different polyether substituents R, whose mixture molecular weight is 450 to 1000 g/mol and whose ethylene oxide content is 70 to 100 mol %, are used here.
  • polyether-modified siloxanes are described which cause improved cell opening.
  • the siloxane contains at least 18 Si units and various side chains are used for modification.
  • EP1873209 describes polyether-modified siloxanes for the production of PU rigid foams with improved fire properties.
  • the siloxanes contain 10 to 45 Si atoms and the polyether side chains consist of at least 90% ethylene oxide units.
  • EP2465891A1 describes polyether-modified siloxanes in which the polyether side chains partially carry OH groups.
  • the siloxanes contain at least 10 Si atoms.
  • EP2465892A1 describes polyether-modified siloxanes in which the polyether side chains mainly carry secondary OH end groups.
  • the siloxanes contain at least 10 Si atoms.
  • Siloxanes are described for use in flexible foam, especially flexible molded foam.
  • Combinations of polyether-modified siloxanes (PES) and polydimethylsiloxanes are described here, with the PES containing 4-15 Si units. No use in rigid foam is described here.
  • Siloxanes that do not contain polyether modification are mainly used in flexible polyurethane foam, especially molded foam, known as additives.
  • EP1095968A1 it describes polydimethylsiloxanes for flexible foam with preferably 7-9 Si atoms
  • DE4444898 C1 it describes the production of cold foams with alkylaryl-modified siloxanes containing 5-16 Si atoms.
  • DE 3215317 C1 describes the production of cold foams with siloxanes that are modified with allyl glycidyl ether and then reacted with amines.
  • the siloxanes contain a maximum of 10 Si atoms.
  • EP0258600A2 describes cold foams with chloropropyl-modified siloxanes with 3-20 Si units and 1-8 side chain modifications.
  • EP2368927A1 describes the production of PU rigid foam using CO 2 as a blowing agent and two different types of polyol, one based on phenolic resins, made from novolaks and alkylene oxides, and one based on aromatic amine polyols, made by alkoxylation of aromatic amines.
  • polydimethylsiloxanes such as hexamethyldisiloxane in particular, can also be used.
  • WO 2015/101497 A1 discloses a composition for producing defect-free PU rigid foams, which is characterized by improved spraying behavior, wherein the composition contains two polyether-modified polysiloxanes of different hydrophilicity.
  • WO 2017/220332 A1 discloses a composition for producing PU rigid foams containing a polyether-modified polysiloxane with a defined content of siloxane units, and a low-boiling hydrocarbon as blowing agent.
  • US$5,852,065 discloses a composition for producing PU foams containing a polysiloxane-based cell opener.
  • US$4,751,251 discloses a composition for producing PU rigid foams containing a polyether-modified polysiloxane and a further additive which is not based on polysiloxanes, e.g. ethoxylated fatty acid alcohols, sulfonates or amides.
  • the object of the present invention was to provide polyurethane or polyisocyanurate rigid foams which have particularly advantageous performance properties, such as in particular low thermal conductivity and/or good surface quality.
  • PAS polyalkyl siloxanes
  • PES polyether-modified siloxanes
  • PU rigid foam-based products such as insulation panels or refrigeration units can be manufactured with higher quality or the manufacturing processes can be made more efficient.
  • polyalkyl siloxanes according to the invention enable corresponding improvements in combination with polyether-modified siloxanes.
  • the polyalkyl siloxanes according to the invention do not contain any polyether modification.
  • the polyalkylsiloxanes according to the invention contain less than 20, preferably less than 15, particularly preferably less than 11 Si atoms.
  • the polyalkyl siloxanes according to the invention are used in combination with polyether-modified siloxanes in a mass ratio of 1:5 to 1:200.
  • the polyalkyl siloxanes and polyether-modified siloxanes according to the invention can be added separately or as a mixture to the mass to be foamed.
  • Suitable carrier media include, for example, glycols, alkoxylates or oils of synthetic and/or natural origin.
  • c + d > 0.5, particularly preferably c + d > 1.
  • R 16 is different from R 11 , R 12 , R 13 , R 14 and R 15 .
  • R 11 , R 12 , R 13 are different, so that the M unit in the siloxane carries two or three different radicals.
  • Preferred polyalkylsiloxanes satisfy the formula 2: wherein R 11 to R 16 and b, c, d are as indicated above.
  • Preferred polyalkylsiloxanes of formula 2 satisfy formulas 3 or 4: therein b, c, d as indicated above.
  • the polyether-modified siloxanes are described in more detail below.
  • R 3 represents the siloxane side chains that can be formed by T and Q units. Since it is not possible to control exactly where these branches are located, R 3 appears again in formula (1) for R 3. This can lead to hyperbranched structures, as occurs, for example, in dendrimers.
  • polyether-modified siloxanes of formula 5 are used, where the molar proportion of oxyethylene units makes up at least 70% of the oxyalkylene units, i.e. x/(x+y) is >0.7. It can also be advantageous if the polyoxyalkylene chain carries a hydrogen or a methyl group at the end and at the same time the molar proportion of oxyethylene units makes up a maximum of 70% of the oxyalkylene units, i.e. x/(x+y) is ⁇ 0.7 and R 5 is a hydrogen or methyl radical.
  • polyether siloxanes of the formula (5) are used in which, inter alia, olefins are used in the hydrosilylation, whereby R 1 consists of at least 10 mol%, preferably at least 20 mol%, particularly preferably at least 40 mol% of CH 2 -R 8 , where R 8 is a linear or branched hydrocarbon having 9 to 17 carbon atoms.
  • polyether siloxanes of the formula (5) are used in which the terminal, or also called alpha and omega, positions on the siloxane are at least partially functionalized with radicals R 1. At least 10 mol%, preferably at least 30 mol%, particularly preferably at least 50 mol% of the terminal positions are functionalized with radicals R 1 .
  • polyether siloxanes of the formula (5) are used in which on average a maximum of 50%, preferably a maximum of 45%, particularly preferably a maximum of 40% of the total average molecular weight of the siloxane is accounted for by the total molecular weight of all, optionally different, radicals R 1 in the siloxane.
  • polyether siloxanes of the formula (5) are used, wherein the number of structural elements with the index n is greater than the number of structural elements with the index m, such that the quotient n/m is at least equal to 4, preferably greater than 6, particularly preferably greater than 7.
  • polyalkyl siloxanes and polyether-modified siloxanes according to the invention can also be used as part of compositions with various carrier media.
  • suitable carrier media include, for example, glycols, alkoxylates or oils of synthetic and/or natural origin. It corresponds to a preferred embodiment of the invention if the total mass fraction of polyalkyl siloxanes and polyether-modified siloxanes according to the invention in the finished polyurethane foam is from 0.01 to 10% by weight, preferably from 0.1 to 3% by weight.
  • the present invention further relates to a composition suitable for producing polyurethane or polyisocyanurate rigid foams, comprising at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and/or isocyanurate catalyst, water and/or blowing agent, and optionally at least one flame retardant and/or further additives, which thereby characterized in that a mixture according to the invention of polyalkyl siloxanes and polyether-modified siloxanes is contained as foam stabilizer, a process for producing polyurethane or polyisocyanurate rigid foams by reacting this composition and the polyurethane or polyisocyanurate rigid foams obtainable thereby.
  • the present invention also relates to the use of polyurethane or polyisocyanurate rigid foams according to the invention as insulating panels and insulation materials, as well as to a cooling apparatus which comprises a polyurethane or polyisocyanurate rigid foam according to the invention as insulating material.
  • the mixture of polyalkyl siloxanes and polyether-modified siloxanes according to the invention has the advantage that they can be used to produce polyurethane or polyisocyanurate rigid foams which are characterized by good fine cell structure and good insulating properties and at the same time have few foam defects.
  • compositions according to the invention which are suitable for producing rigid polyurethane or polyisocyanurate foams contain at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and/or isocyanurate catalyst, water and/or blowing agent, and optionally at least one flame retardant and/or further additives, and are characterized in that at least one mixture according to the invention of polyalkyl siloxanes and polyether-modified siloxanes is contained.
  • the mass fraction of siloxane mixture according to the invention (i.e. polyalkyl siloxanes and polyether-modified siloxanes) d) based on 100 parts by mass of polyol component a) is preferably from 0.1 to 10 pphp, more preferably from 0.5 to 5 pphp and particularly preferably from 1 to 3 pphp.
  • Polyols suitable as polyol component a) within the meaning of the present invention are all organic substances having one or more groups reactive towards isocyanates, preferably OH groups, and their preparations.
  • Preferred polyols are all those commonly used for the production of polyurethane systems, in particular polyurethane coatings, polyurethane elastomers or foams; polyether polyols and/or polyester polyols and/or aliphatic polycarbonates containing hydroxyl groups, in particular polyether polycarbonate polyols and/or polyols of natural origin, so-called "natural oil based polyols" (NOPs).
  • the polyols usually have a functionality of 1.8 to 8 and number-average molecular weights in the range from 500 to 15,000.
  • the polyols with OH numbers in the range from 10 to 1200 mg KOH/g are usually used.
  • Polyether polyols can be produced by known processes, for example by anionic polymerization of alkylene oxides in the presence of alkali hydroxides, alkali alcoholates or amines as catalysts and with the addition of at least one starter molecule which preferably contains 2 or 3 reactive hydrogen atoms bonded to it, or by cationic polymerization of alkylene oxides in the presence of Lewis acids such as antimony pentachloride or boron trifluoride etherate or by double metal cyanide catalysis.
  • Suitable alkylene oxides contain 2 to 4 carbon atoms in the alkylene radical.
  • Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide; ethylene oxide and 1,2-propylene oxide are preferably used.
  • the alkylene oxides can be used individually, cumulatively, in blocks, alternately one after the other or as mixtures.
  • Starter molecules used are in particular compounds with at least 2, preferably 2 to 8 hydroxyl groups or with at least two primary amino groups in the molecule.
  • Starter molecules used can be, for example, water, 2-, 3- or 4-hydric alcohols such as ethylene glycol, propanediol-1,2 and -1,3, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, in particular sugar compounds such as glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resoles, such as oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines as well as melamine, or amines such as aniline, EDA, TDA, MDA and PMDA, particularly preferably TDA and PMDA.
  • the choice of the appropriate starter molecule depends on the respective application area of the resulting polyether polyol in polyurethane production
  • Polyester polyols are based on esters of polybasic aliphatic or aromatic carboxylic acids, preferably with 2 to 12 carbon atoms.
  • aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fumaric acid.
  • aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • polyester polyols are obtained by condensation of these polybasic carboxylic acids with polyhydric alcohols, preferably diols or triols with 2 to 12, particularly preferably with 2 to 6 carbon atoms, preferably trimethylolpropane and glycerol.
  • polyester polyols based on aromatic carboxylic acids are used in more than 50 pphp, preferably more than 70 pphp, based on 100 parts by mass of polyol component.
  • no polyols based on phenolic resins produced from novolaks and alkylene oxides and no polyols based on aromatic amine polyols produced by alkoxylation of aromatic amines are used, which means that in this preferred embodiment less than 20 pphp, preferably less than 10 pphp, in particular less than 2 pphp, and most advantageously no polyols based on phenolic resins produced from novolaks and alkylene oxides and no polyols based on aromatic amine polyols produced by alkoxylation of aromatic amines are used.
  • Polyether polycarbonate polyols are polyols that contain carbon dioxide bound as carbonate. Since carbon dioxide is produced in large quantities as a by-product in many processes in the chemical industry, the use of carbon dioxide as a comonomer in alkylene oxide polymerizations is of particular interest from a commercial point of view. Partially replacing alkylene oxides in polyols with carbon dioxide has the potential to significantly reduce the costs of producing polyols. In addition, the use of CO2 as a comonomer is ecologically very advantageous, since this reaction represents the conversion of a greenhouse gas into a polymer. The production of polyether polycarbonate polyols by adding alkylene oxides and carbon dioxide to H-functional starter substances using catalysts has long been known.
  • the first generation consisted of heterogeneous zinc or aluminum salts, as used, for example, in US-A 3900424 or US-A 3953383
  • mono- and binuclear metal complexes have been successfully used for the copolymerization of CO2 and alkylene oxides ( WO 2010/028362 , WO 2009/130470 , WO 2013/022932 or WO 2011/163133 ).
  • the most important class of catalyst systems for the copolymerization of carbon dioxide and alkylene oxides are the double metal cyanide catalysts, also known as DMC catalysts ( US-A 4500704 , WO 2008/058913 ).
  • Suitable alkylene oxides and H-functional starter substances are those which are also used for the production of carbonate-free polyether polyols - as described above.
  • Polyols based on renewable raw materials "Natural oil based polyols” (NOPs) for the production of polyurethane foams are of increasing interest in view of the long-term limited availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices and have already been described many times in such applications ( WO 2005/033167 ; US2006/0293400 , WO 2006/094227 , WO 2004/096882 , US2002/0103091 , WO 2006/116456 and EP1678232 ).
  • a number of these polyols are now available on the market from various manufacturers ( WO2004/020497 , US2006/0229375 , WO2009/058367 ).
  • polyols Depending on the base raw material (e.g. soybean oil, palm oil or castor oil) and the subsequent processing result in polyols with different properties.
  • base raw material e.g. soybean oil, palm oil or castor oil
  • Two main groups can be distinguished here: a) Polyols based on renewable raw materials that are modified to such an extent that they can be used 100% for the production of polyurethanes ( WO2004/020497 , US2006/0229375 ); b) polyols based on renewable raw materials, which, due to their processing and properties, can only replace the petrochemically based polyol to a certain extent ( WO2009/058367 ).
  • polystyrene polyols Another class of polyols that can be used are the so-called filler polyols (polymer polyols). These are characterized by the fact that they contain solid organic fillers up to a solids content of 40% or more in dispersed distribution.
  • SAN, PHD and PIPA polyols can be used, among others.
  • SAN polyols are highly reactive polyols that contain a dispersed copolymer based on styrene/acrylonitrile (SAN).
  • PHD polyols are highly reactive polyols that also contain polyurea in dispersed form.
  • PIPA polyols are highly reactive polyols that contain a polyurethane in dispersed form, for example formed by the in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
  • polyols that can be used are those that are obtained as prepolymers by reacting polyol with isocyanate in a molar ratio of preferably 100:1 to 5:1, preferably 50:1 to 10:1.
  • prepolymers are preferably prepared dissolved in polymer, the polyol preferably corresponding to the polyol used to prepare the prepolymers.
  • a preferred ratio of isocyanate and polyol, expressed as an index of the formulation, i.e. as the stoichiometric ratio of isocyanate groups to groups reactive towards isocyanate (e.g. OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000, preferably 40 to 600.
  • An index of 100 represents a molar ratio of the reactive groups of 1 to 1.
  • the index of the formulation is in the range 150 to 550, particularly preferably 200 to 500. This means that there is a significant excess of isocyanate groups to isocyanate-reactive groups. This leads to trimerization reactions of the isocyanates, which thus form isocyanurates.
  • foam types are also referred to as polyisocyanurate (PIR) foams and are characterized by improved fire behavior, i.e. poorer burning.
  • One or more organic polyisocyanates with two or more isocyanate functions are preferably used as isocyanate components b).
  • One or more polyols with two or more isocyanate-reactive groups are preferably used as polyol components.
  • Isocyanates suitable as isocyanate components in the context of this invention are all isocyanates that contain at least two isocyanate groups.
  • all known aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates can be used.
  • Isocyanates in a range of 60 to 200 mol% relative to the sum of the isocyanate-consuming components are particularly preferably used.
  • alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, and preferably hexamethylene-1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanato-methyl-cyclohexane (isophorone diisocyanate or IPDI for short), 2,4- and 2,6-hexahydrotoluylene diisocyanate and the corresponding isomer mixtures, and preferably aromatic di- and polyisocyanates,
  • the organic di- and polyisocyanates can be used individually or in the form of their mixtures.
  • Corresponding "oligomers" of the diisocyanates can also be used (IPDI trimer based on isocyanurate, biuret-urethdiones).
  • IPDI trimer based on isocyanurate, biuret-urethdiones.
  • prepolymers based on the above-mentioned isocyanates is also possible.
  • modified isocyanates It is also possible to use isocyanates that have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, so-called modified isocyanates.
  • Particularly suitable organic polyisocyanates and therefore particularly preferred are various isomers of toluene diisocyanate (2,4- and 2,6-toluene diisocyanate (TDI), in pure form or as isomer mixtures of different compositions), 4,4 ⁇ -diphenylmethane diisocyanate (MDI), the so-called “crude MDI” or “polymeric MDI” (contains not only the 4,4 ⁇ - but also the 2,4 ⁇ - and 2,2 ⁇ -isomers of MDI and higher-nuclear products) and the binuclear product known as "pure MDI” consisting mainly of 2,4 ⁇ - and 4,4 ⁇ -isomer mixtures or their prepolymers.
  • TDI toluene diisocyanate
  • MDI 4,4 ⁇ -diphenylmethane diisocyanate
  • the so-called “crude MDI” or “polymeric MDI” contains not only the 4,4 ⁇ - but also the 2,4 ⁇
  • isocyanates are, for example, in EP1712578 , EP1161474 , WO 00/58383 , US2007/0072951 , EP1678232 and the WO 2005/085310 , all of which are incorporated herein by reference.
  • Suitable catalysts c) in the sense of the present invention are all compounds that are able to accelerate the reaction of isocyanates with OH functions, NH functions or other isocyanate-reactive groups as well as with isocyanates themselves.
  • Customary catalysts known from the prior art can be used, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of tin, iron, bismuth and zinc.
  • amines cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups
  • ammonium compounds preferably those of tin, iron, bismuth and zinc.
  • mixtures of several components can be used as catalysts.
  • the mixtures of siloxanes according to the invention i.e. polyalkyl siloxanes and polyether-modified siloxanes are used.
  • PES polyether-modified siloxanes
  • PAS polyalkylsiloxanes
  • PES polyether-modified siloxanes
  • the total amount of siloxanes used is such that the mass fraction based on the finished polyurethane is 0.01 to 10 wt.%, preferably 0.1 to 3 wt.%.
  • blowing agents e is optional, depending on the foaming process used. Chemical and physical blowing agents can be used. The choice of blowing agent depends largely on the type of system.
  • a foam with a high or low density is produced.
  • Foams with densities of 5 kg/m 3 to 900 kg/m 3 can be produced.
  • Preferred densities are 8 to 800, particularly preferably 10 to 600 kg/m 3 , in particular 30 to 150 kg/m 3 .
  • Physical blowing agents can be compounds with suitable boiling points. Chemical blowing agents containing NCO groups can also be used. and release of gases, such as water or formic acid.
  • propellants are liquefied CO2, nitrogen, air, highly volatile liquids, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, hydrofluoroolefins (HFO) or hydrohaloolefins such as 1234ze, 1234yf, 1233zd(E) or 1336mzz, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
  • Suitable water contents within the meaning of this invention depend on whether or not one or more blowing agents are used in addition to the water.
  • preferred values are typically 1 to 20 pphp; if other blowing agents are also used, the preferred amount used is usually reduced to 0.1 to 5 pphp.
  • additives f all substances known in the art which are used in the production of polyurethanes, in particular polyurethane foams, such as crosslinkers and chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, emulsifiers, etc. can be used.
  • the process according to the invention for producing PU foams can be carried out using known methods, for example by hand mixing or preferably with the aid of foaming machines. If the process is carried out using foaming machines, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out both discontinuously and continuously.
  • a preferred polyurethane or polyisocyanurate rigid foam formulation within the meaning of this invention results in a density of 5 to 900 kg/m3 and has the composition stated in Table 1.
  • Table 1 Composition of a preferred polyurethane or polyisocyanurate rigid foam formulation component Weight percentage Polyol 0.1 to 100 Amine catalyst 0 to 5 Metal catalyst 0 to 10 Polyalkyl siloxanes and polyether-modified siloxanes 0.1 to 5 Water 0.01 to 20 Propellant 0 to 40 Other additives (flame retardants etc.) 0 to 90 Isocyanate index: 10 to 1000
  • Another object of the invention is a PU rigid foam obtainable by the said process.
  • the rigid polyurethane foam has a density of 5 to 900 kg/m 3 , preferably 8 to 800, particularly preferably 10 to 600 kg/m 3 , in particular 30 to 150 kg/m 3 .
  • Rigid polyurethane foam or PU rigid foam is a fixed technical term.
  • the known and fundamental difference between soft foam and rigid foam is that soft foam exhibits elastic behavior and thus the deformation is reversible.
  • Rigid foam on the other hand, is permanently deformed.
  • rigid polyurethane foam is understood to mean in particular a foam according to DIN 7726, which has a compressive strength according to DIN 53 421 / DIN EN ISO 604 of advantageously ⁇ 20 kPa, preferably ⁇ 80 kPa, preferably ⁇ 100 kPa, more preferably ⁇ 150 kPa, particularly preferably ⁇ 180 kPa.
  • the rigid polyurethane foam according to DIN ISO 4590 advantageously has a closed cell content of greater than 50%, preferably greater than 80% and particularly preferably greater than 90%.
  • the PU rigid foams according to the invention can be used as or for the production of insulating materials, preferably insulation boards, refrigerators, insulating foams, roof liners, packaging foams or spray foams.
  • the PU foams according to the invention can be used to advantage in particular in the cold storage, refrigeration equipment and household appliance industries; e.g. for the production of insulation panels for roofs and walls, as insulating material in containers and warehouses for frozen goods and for refrigerators and freezers.
  • Cooling apparatuses according to the invention have a PU rigid foam (polyurethane or polyisocyanurate foam) according to the invention as insulating material.
  • a further object of the invention is the use of PU rigid foam as insulation material in refrigeration technology, in refrigerated furniture, in the construction, automotive, shipbuilding and/or electronics sectors, as insulation boards, as spray foam, as one-component foam.
  • PAS polyalkyl siloxanes
  • M a D b T c Q d , as defined above.
  • Table 2 Description of polyalkyl siloxanes Example a b c d R11 R12 R13 R14 R15 R16 PAS No. 1 3 0 1 0 Me Me Me Me - - Me PAS No. 2 3 0 1 0 Me Me Me Me - - vinyl PAS No. 3 4 0 0 1 Me Me Me Me - - - PAS No. 4 4 0 2 0 Me Me Me Me - - Me PAS No. 5 2 1 0 0 Me Me Me Octyl Me - PAS No.
  • polyether-modified siloxane and polyalkyl siloxanes were used in mixture or combination.
  • Table 3 Description of PAS/PES blends (overview of PES/PAS combinations Mixtures PES Weight share PAS Weight share Mixture 1 number 1 98 number 1 2 Mixture 2 number 1 98 No. 8 2 Mixture 3 number 1 98 No. 10 2 Mixture 4 No. 2 98 number 1 2 Mixture 5 No. 2 98 No. 2 2 Mixture 6 No. 2 98 No. 3 2 Mixture 7 No. 2 98 No. 4 2 Mixture 8 No. 2 98 No. 5 2 Mixture 9 No. 2 98 No. 6 2 Mixture 10 No. 2 95 No. 7 5 Mixture 11 No. 2 98 No. 10 2 Mixture 12 No. 2 98 No. 11 2 Mixture 13 No.
  • the foaming was carried out using a manual mixing method.
  • the compounds according to the invention, polyols, flame retardants, catalysts, water, siloxane surfactants according to the invention or not according to the invention, polyalkyl siloxanes according to the invention and blowing agents were weighed into a beaker and mixed with a plate stirrer (6 cm diameter) was mixed for 30 s at 1000 rpm.
  • the amount of blowing agent that evaporated during the mixing process was determined by weighing again and then replenished.
  • the isocyanate (MDI) was then added and the reaction mixture was stirred with the stirrer described for 5 s at 3000 rpm.
  • the mixture was immediately poured into an aluminum mold measuring 50 cm x 25 cm x 7 cm and thermostatted to 65°C.
  • the amount of foam formulation used was such that it was sufficient to fill the mold to a minimum.
  • the foams were demolded after 10 minutes and then stored at room temperature for 24 hours.
  • the thermal conductivity ( ⁇ value in mW/m ⁇ K) was measured on 2.5 cm thick panes using a Hesto Lambda Control device, model HLC X206, at an average temperature of 10°C in accordance with the specifications of the EN12667:2001 standard.

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